Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
  • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
  • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom

Definitions

• R1 to R3 are hydrogen, halogen, branched or unbranched C1-C6-alkyl, C1-C8-alkoxy, C1-C6-haloalkyl, C1-C6-haloalkoxy, nitro, cyano, phenyl or one to three times with C1-C4-alkyl , Halogen, C1-C5-haloalkyl, C1-C4-alkoxy or C1-C5-haloalkoxy-substituted phenyl; X -OR4 or -NH-OR5, R4 branched or unbranched C3-C10 alkynylalkyl which may be unsubstituted or substituted by halogen; R5 branched or unbranched C1-C5 alkyl which is unsubstit
• the invention relates to a process for the preparation of the thiophene-2-carboxylic acid derivatives I and their use for controlling unwanted vegetation.
• the invention had for its object to provide new thiophene-2-carboxylic acid derivatives with good herbicidal activity. Furthermore, the task was to find new biological effects in known pesticides.
• R1 - R3 Hydrogen such as fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine
• C1-C6-alkyl especially C1-C4-alkyl such as methyl, ethyl, ios-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl
• C1-C8 alkoxy especially C1-C4 alkoxy such as methoxy, ethoxy, propyloxy, 1-methylethoxy, butoxy, 1-methylpropyloxy, 2-methylpropyloxy and 1,1-dimethylethoxy
• C1-C6-haloalkyl especially C1-C4-haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl,
• R 1, R 2 and R 3 are particularly preferably hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, isopropl, cyclopropyl, methoxy, ethoxy, isopropyloxy, chloromethyl, trifluoromethyl, trifluoromethoxy and phenyl, which may be mono- to trisubstituted can with halogen or alkyl and substituted alkyl functions such as the above, for example 4-chlorophenyl, 3,5-dichlorophenyl, 3-trifluoromethylphenyl, 4-methoxyphenyl or 2-fluoro-4-chlorophenyl; R4 branched or unbranched C3-C10 alkynylalkyl, in particular C3-C6alkynylalkyl, such as 2-propynyl, 3-butynyl, 3-butyn-2-yl, 4-pentynyl, 1-pentyn-3-yl, 2-
• R5 C1-C5-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec. Butyl, tert-butyl or pentyl and the radicals listed under R4.
• the thiophene-2-carboxylic acids required as starting substances are known or can be prepared by generally known chemical processes (see Heterocyclic Compounds, Thiophene and its Derivatives, Vol. 44, Part 1, pp. 1 ff, New York 1985 or US-A 3,536,473 ) produce.
• the thiophene carboxylic acid halides, of which the chlorides are particularly preferred, can be obtained in a known manner, for example as in Houben-Weyl, Methods of Organic Chemistry p. 463 ff, from the corresponding carboxylic acids.
• alkynols R4OH are known from the literature, are commercially available or e.g. as described in Houben-Weyl, Methods of Organic Chemistry, Volume 6 / 1a, Part 2, pp. 1078-1090, 1980.
• the esterification of the acid can be carried out in a manner known per se, e.g. as described in Houben-Weyl, Methods of Organic Chemistry, Volume VIII, p. 516 ff, Georg Thieme Verlag, Stuttgart 1952.
• catalysts such as sulfuric acid, hydrogen halide, sulfonic acid, acidic ion exchange
• the reaction can be accelerated or the esterification equilibrium shifted in the desired sense by removing the reaction products from the reaction mixture, for example by removing the water by azeotropic distillation or a dehydrating agent such as dicyclohexylcarbodiimide adds.
• Acid acceptors are common basic agents, especially aliphatic, aromatic and heterocyclic amines, e.g. Triethylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, lutidine, 4-dimethylaminopyridine.
• Alkali metal carbonates such as sodium or potassium carbonate are also suitable as acid acceptors.
• the reaction can be carried out in a solvent or diluent.
• the acid acceptors mentioned themselves or the following solvents or diluents or mixtures thereof are partially suitable for this purpose:
• Aliphatic and aromatic, optionally chlorinated hydrocarbons such as petroleum ether, benzene, toluene, xylene, gasoline, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane, chlorobenzene, ethers such as diethyl and di-n-butyl ether, methyl tert-butyl ether , Tetrahydrofuran, dioxane; Ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone; also nitriles such as acetonitrile and propionitrile.
• hydrocarbons such as petroleum ether, benzene, toluene, xylene, gasoline, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane, chlorobenzene, ethers such as diethyl and di-n-butyl ether,
• the starting materials are usually used in a stoichiometric ratio. However, an excess of one or the other can be advantageous in individual cases.
• the thiophenecarboxylic acid esters according to the invention can also be prepared by practically all known processes of ester synthesis, for example by reacting corresponding carboxylic acid salts with propargyl halides, by transesterification reactions (cf. Houben-Weyl loc. Cit., Pp. 508 to 628; C. Ferri, Reactions in Organic Synthesis, pp. 446 ff, Georg-Thieme-Verlag, Stuttgart 1978; S. Patai, The Chemistry of Carboxylic Acids and Esters, p. 505 55, Interscience Publishers, London 1969).
• the acid amides can be prepared by aminolysis of thiophene-2-carboxylic acids in a known manner, for example as described in Houben-Weyl, Methods of Organic Chemistry, Volume E5, Part 2, 4th Edition, p. 1144ff.
• the thiophene-2-carboxylic acid derivatives I or the herbicidal compositions comprising them can be carried out, for example, in the form of directly sprayable solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules Spraying, atomizing, dusting, scattering or pouring can be used.
• the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
• Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water.
• the substrates as such or dissolved in an oil or solvent, by means of wetting, adhesive, dispersing or emulsifying agents medium homogenized in water.
• concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
• alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol, tributylphenyl poly
• Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
• Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
• Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
• the formulations generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient.
• the agents can be applied pre-emergence or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can also be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active ingredients are more undesirable on the leaves below them Plants or the uncovered floor area (post-directed, lay-by).
• the application rates of active ingredient are 0.001 to 3 kg / ha, preferably 0.01 to 1 kg / ha.
• the compounds according to the invention can be used in a large number of crop plants.
• the following crops are considered, for example:
• the thiophene-2-carboxylic acid derivatives of the formula I can be mixed with one another and also with representatives of other herbicidal or growth-regulating active compound groups and applied together.
• thiophene-2-carboxylic acid derivatives of the formula I or herbicidal compositions containing them alone or in combination to be mixed with other herbicides or with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria.
• other herbicides or with other crop protection agents for example with agents for controlling pests or phytopathogenic fungi or bacteria.
• miscibility with mineral salt solutions which are used to remedy nutritional and trace element deficiencies.
• Non-phytotoxic oils and oil concentrates can also be added.
• Plastic flower pots with a content of 300 cm3 and loamy sand with about 3.0% humus serve as culture vessels.
• the seeds of the test plants are sown separately according to species.
• plants are either sown directly or grown in the same containers, or they are first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
• test plants are then treated at a height of 3 to 15 cm with the active ingredients suspended or emulsified in water as a distribution medium and sprayed through finely distributing nozzles.
• the application rate for post-emergence treatment is 1.0 kg / ha a.S. (active substance).
• test vessels are set up in the greenhouse, warmer areas (20 to 35 ° C.) being preferred for heat-loving species and 10 to 20 ° C. being preferred for those with moderate climates.
• the trial period spans 2 to 4 weeks. During this time, the plants are cared for and their reaction to the individual treatments is evaluated.
• Evaluation is based on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
• the plants used in the greenhouse experiments consist of the following types: abbreviation Latin name German name AMARE Amaranthus retroflexus Curved foxtail CHEAL Chenopodium album White goose foot CHYCO Chrysantemum corinarium Crown usury flower HELAN Helianthus annuus Sunflower ORYZA Oryza sativa rice

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Heterocyclic Compounds Containing Sulfur Atoms (AREA)
• Plural Heterocyclic Compounds (AREA)

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• 1989
  • 1989-01-16 DE DE3901074A patent/DE3901074A1/de not_active Withdrawn
• 1990
  • 1990-01-04 DE DE59008324T patent/DE59008324D1/de not_active Expired - Lifetime
  • 1990-01-04 EP EP90100149A patent/EP0379003B1/fr not_active Expired - Lifetime
  • 1990-01-09 US US07/463,163 patent/US5034049A/en not_active Expired - Fee Related
  • 1990-01-09 CA CA002007394A patent/CA2007394A1/fr not_active Abandoned
  • 1990-01-16 JP JP2004674A patent/JPH02229187A/ja active Pending

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